Paul bottigeb



"UNITED STATES PATENT @nnis PAUL no'rTIenn, on LODZ, RUSSIA, ASSIGNOR ro THE AcTInNeEsutLscHAFT I run ANILIN FABRIKATION, OF BERLIN, GERMANY,

MANUFACTURE OF NEW RED DYE-STUFFS OR COLORING-MATTERS.

SPECIFICATION forming part of Letters Patent No. 365,666, dated June 2.9 1887.

Application filed November 22, 1884 Serial No. 148,595. (No specimens.) Patented in Germany February 27, 1984, No. 28,753; in

I jrancc March 4, 1884, No. 166,722, and in England March 5, .1884, No. 1, 1l5.

To aZZ whom it may concern-.-

Be it known that I, PAUL BoTTIG ER, a subject of the King of Saxony, Germany, residing at the city of Lodz, in the Empire of Russia, have invented certain new and useful Immovements: in the Manufacture of Red Dyev contact aqueoussolutions'of tetrazo-diphenyl salts with aqueous solutions of alpha or beta naphthylamines, or with aqueous solutions of, salts of the various sulpho-acids' ofalphaf or beta naphthylamines. Instead of aqueous solutions of-naphthylamine salts, there may be uscdyalcoholic solutions of alpha or beta naphthylamingor alpha or beta naphthyl amine or their salts finely divided in water]v The result of the combination of-tetrazo-diphe-' nyl-with both 'naphthylamines are dye-stuffs which are insoluble in water, but soluble in alcohol, andwhieh form their respective mono and disulpho acids by treatment with concentrated sulphuric acid, anhydrous sulphuric acid, fuming sulphuric acid, or monochlorhybluish-red dye-stufls which water.

drine. The alkali salts of the thus-formed mono and disulpho acids are yellowish-red or aresoluble in \Vhen alpha-naphthylamine is used,red dye-- Tetrazo-diphenyl' Naphthylamine The salts of tetrazo-diphenyl are formed, as 4 Eleample 1.-'-25.7 kilos of hydrochlorate of :r

chloride stuffs are formed, while betanaphthylamine, in combination with tetrazo-dipheuyl, yields yellowish-red dye-stuffs. \Vhen tetrazo-diphcnyl is'coinbined with the Slllpl'lO-ftOlflS of alpha or beta naphthylaminc, substances are formed that dissolve in water which is free of acid,

and whose alkali salts form also yellowishred 60, ing an aqueous solution, of a totrazo'diphenyl tions of the new dye-stuffs are obtained, or by adding an aqueous solution of a tetrazodiphenyl salt to an alcoholic solution of naphthyh amine sulpho-acid,or to naphthylaminesulphoacid finely divided in water. T s reactionthat is to say, the formation of the new dyestuffis, however, going on in the easiest manner if a solution of a tetrazo-diphenyl salt of one of the various sulpho-aeids of alpha or beta naphthylamine is used, to which. solutionrthe required amount of sodium acetate has been added, so as to prevent the presence of free strong mineral acids-such as sulphuric or hydrochloric acids-after the solutions have been mixed, while some free acetic acid is left in the solution; but even then the formation of the new dyestuffs does not take place, in

stantly, but gradually, and requires several hours before the reaction is completed.

The new dye-stuffs are formed by combining one molecule of tetrazo-diphenyl with two molecules of alpha orbeta naphthylamine or alpha or beta naphthylamine sulpho-aeid,

according to the following equation:

A O HN=NC H,NH.HO1 21101 t O2HiN=NO$HZNHZHGl Ohlorhydrate of the new dye-stuffs, (hi-LN=NG,,,H,SO,'1INH,g l 0,, H,N=NO,,H,SO,1TIN H New dye-stuffs.

- ZNaCl-l- 5 tweni'ry per cent. of anhydrous acid. The mixture is then'raised to a temperature of 30 centigrade until a sample taken from the salt of benz idine',-=are finely'divi'dedv-in-five hundred litersof water'containing thirty kilos of hydrochloric acid of 209Baum. To this is added under continuous stirring, and in small portions, a solution of 13.8 kilos of sodium nitrite of one hundred per cent. in one hundred and fifty liters of water.

The salts of benzidine to be diazotized should not be used in a dry state, but in the shape of a moist paste, as' the reaction takes place slowly and imperfectly with dry benzidine salts. The benzidine salt dissolves and forms a solutionof tetrazo diphen'y'l chloride. This solution is poured under continuous stirring into a solution of 36.5 kilos of hydrochlorate of alpha-naphthylamine in two thousand liters of water. A precipitate is formed at once, which, after settling for several hours, is decanted from the mother-1i quor. It is then washed and dried. In orderto transform the thus formed dye-stuff, which is soluble in alcohol, into its monosulphoacid, twenty-five kilos of the dye-stul't'arc finely. ground and sifted, and then slowly mixed, while exposed to. cooling, with seventy-five kilos of fuming sulphuric acid containing molten mass dissolves entirely in water containing some ammonia. When this point of s'olubilityis reached, the mass is mixed under 7 continuous stirring with about one thousand .,wel1-knlown manner.

,- liters of water. The sulpho-acid formed thereby settles as a precipitate. themother-liquor by decanting and then trans- It is separated from formed into a sodium-or'a'mmoniumsalt in the In order to produce a disulpho-'acid of the substance formed by the combination of tetrazo-diphenyl with alphanaphthylami'ne, twenty-five kilos of thesamc' are mixed'with;seveuty='fi.ve kilos of fuming sulphuric .acid containing twenty per cent. anhydrous acid,while the mixture is kept cool.

' Seventy-five kilos of fuming sulphuric acid for about an hour.

into about three thousand liters of water and containing twenty per cent. of anhydrous acid are then added and the mixture heated and kept at a temperature of to-"dO centigrade The molten mass is poured then boiled; next saturated with milk cf lime and filtered. The calcium salt of thedis ulphoacid contained in the filtered liquid is decomposed by either sodium'or ammon um carbon- Thus solutions of the ammonium orsodium salts of the disulpho-acid of the alpha:

ate.

amitlo-naphthaline tetrazo-diphenyl are obtained, which, after being mechanically'separated from the calcium carbonate,'are evaporated to dryness, or the salts are obtained therefrom in, the well-known manner by evaporation and treatment with common. salt.

Example 2.-25.7 kilos of chlorhydrate of benzidine, or 28.2 kilos sulphate ofbenzidine,

or an equivalent amount of some other :saltof benzidinc, are diazotized in the same way as described in, the first example. The'thus-resulting solution of tctrazo-diphenyl 'chlorlde is slowly po red under continuous stirring into one thousand liters of water containlng fifty-five kilos of sodium naphthion'ate and twelve kilos of sodium acetate." After having settled for about twelve hours the thus-formed paste of dye-stuffs is mechanically separated I fromthe mothcr-liquorand subsequentlytransformed in the usual manner into. a sodium or ammonium salt and afterward dried. The

thus-producr :l new dye-stuff imparts a perma-' nent red color to wool and cotton, tl1e latter taking it without the use of any mordants,

. Having thus described my inventioinl claim as new and desire to secure by LettersPatcnt- The process herein described of making new red dye-stuffs, which consists, first, in 'co'mbining the salts of tetrazo diphenylwith alpha or beta naphthylamines, and, secondlyyiirtreating the thusformed dye-stuffs with concen-v trated sulphuric acid, anhydroussulphuric PAUL Bernese;

acid, or monochlcrhydrinc, wherebythe-mono or disulpho itclLlS of said dye-stuffs or thesalts of said acids are obtained,substantially asset whereof I have'sign y thei'presenceof 3 

